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AN ACCOUNT OF THE PROGRESS 

I 

TAT / 


CHEMISTRY 


IN 

THE YEAR 18.8 2. 


• 


PROF. H. CARRINGTON BOLTON. 


FROM THE SMITHSONIAN REPORT FOR 1882. 




* 



WASHINGTON: 
GOVERNMENT PRINTING OFFICE. 

1883. 



53© 



AN ACCOUNT OF THE PROGRESS 



IN 



CHEMISTEY 



IN 



THE YEAR 1882 



BY 



PROF. H. CARRINGTON BOLTON. 

1t 



FROM THE SMITHSONIAN REPORT FOR 1882. 



WASHINGTON: 

GOVERNMENT PRINTING OFFICE. 

1883. 






^ 






\ 







CHEMISTRY. 



By H. Carhington Bolton, Ph. D., 

Professor of Chemistry in Trinity College, Hartford, Conn. 



The year 1882 is marked by great industry in all departments of 
•chemistry; no startling announcements have been made, but several 
extremely interesting syntheses of organic bodies have been accom- 
plished, viz, tyrosine and uric acid, both of the animal organism. Great 
activity is noted in the revision of the atomic weights. Progress has 
been made in unraveling the knotty problem of the rare earths in cerite, 
samarskite, and gadolinite, but no satisfactory conclusions have been 
reached as to the existence of the larger number of elementary bodies 
announced since 1877. 

In the brief space at our disposal we can barely note the salient fea- 
tures of the year's work in a series of short abstracts, and these we con- 
fine chiefly to pure chemistry, paying little attention to analytical and 
industrial chemistry. Periodical literature, devoted exclusively to chem- 
istry and its applications, is becoming voluminous ; the fifteen principal 
journals of America, England, France, and Germany publish annually 
about 18,000 pages; in this rough estimate journals of physics and 
transactions of societies are not included, and both classes of serials 
contain much chemical'material. We need hardly say that no attempt 
is made in the following pages to chronicle the prodigious amount and 
variety of work contained in these and other sources of information. 

INORGANIC CHEMISTRY. 

On the Reciprocal Solutions of Liquids. — Wladimii? Alexejeff has de- 
voted eight years to a study of the mutual solutions of mixed liquids, 
and he finds that the hypothesis proposed by Dossios is subject to ex- 
ceptions. The latter stated that the mutual solubility of liquids in- 
creases with the rise in temperature, but Alexejeft finds that in certain 
bodies (isobutyl alcohol, for example) the solubility diminishes with an 
increase of temperature. He also discovers that the solubility decreases 
to a definite point and then increases again, or, in other words, that a 
minimum of solubility exists, just as certain solids have a maximum of 
solubility. 

When phenol and water are brought together two layers form; the 
lower is a solution of phenol in water, the upper a solution of water in 



2 SCIENTIFIC RECORD FOR 1882. 

phenol. Now the mutual solubility of these liquids increases with the. 
temperature, and at a certain point (68° for pure phenol) the two liquids 
mix in all proportions. Many liquids, such as aniline and water, follow 
the same law ; solids, too, obey the same law, as is shown by the mutual 
action of water and salicylic acid. The author claims that the solutions 
of solid and of liquid salicylic acid exhibit a true physical isomerism. 
(Bull. Soc. Ghim., xxxviii, p. 145.) 

Molecular Structure and Physical Properties.— That a close connection 
exists between the structure of molecules and the physical properties 
of the substances composed of these molecules is becoming more and 
more evident. Pawlewski finds that the "critical temperatures" of 
isomeric ethers are very nearly identical, and that isomers containing 
doubly-linked atoms of carbon have a higher critical temperature than 
those in the molecules of which the carbon atoms are singly linked. 
(Berichte d. chem. Ges., XV, p. 460.) 

Determination of Gas Densities. — H. Goldschmidt and Victor Meyer 
have devised a simple method for determining gas densities in an expe- 
ditious manner. The process was employed at first in connection with 
experiments made on the density of cyanogen at various temperatures^ 
but is applicable to many bodies. The vessel employed is first filled 
with pure, dry air of the temperature at which the density is to be 
taken ; the air is then displaced by hydrochloric acid gas (free from air),, 
collected over water and measured. The hydrochloric acid gas is in 
turn replaced by air. The gas to be examined is then introduced until 
all the air is expelled, and this gas is again displaced by hydrogen, or 
by air, and collected in a potash bulb containing a liquid capable of 
completely absorbing it. The increase in weight of the potash bulb 
gives the weight of the gas ; the weight of an equal volume of air at the 
same temperature is determined from the volume collected, and the 
quotient gives the density sought. 

The apparatus consists of a glass cylinder 200 mm long, 30 mm in diam- 
eter, with a capillary tube at each end, the extremities of which tubes 
rise above the upper end of the cylinder and are bent at right angles. 
This apparatus is heated in a glass tube with a bulbous extremity 
400 mm long, and of sufficient size to contain the liquid, whose boiling 
point is the temperature of measurement. The liquids used in the outer 
vessel are water, aniline, amyl benzoate, and diphenylamine. For 
higher temperatures boiling sulphur and penta-sulphide of phosphorus 
are used, in which case the inner vessel receives a spherical form, and 
the outer vessel is made of iron. 

The authors obtained by this process a density of 1.53 for carbonic 
anhydride, and of 1.26 for hydrochloric acid gas, figures exactly equal 
to the theoretical values. 

The apparatus can also be employed as an air thermometer. Sulphur 
was found to boil at 426° C. (Berichte d. chem. Ges., XV, p. 137.) 



CHEMISTRY. 6 

Chemical Reactions in the Leclanche Cell. — Dr. Edward Divers has 
presented the following reactions : Zinc is slowly acted upon by a solu- 
tion of ammonium chloride, and crystals of zinco-diammonium-chloride 
are formed ; this is decomposed by water alone into an insoluble and a 
soluble portion, probably as shown in this equation : 

3Zn (NH 3 Cl) 2 + 2 OH 2 = 2 HO Zn NH 3 01 + (01 H 4 1ST),. Zn (NH 3 01) 2 
Zinco-diammonium-chloride dissolved in solution of ammonium chlo- 
ride acts gradually on artificially prepared hydrogen manganite, H 2 4 
Mn 2 , causing manganese to go into solution, and the precipitation of 
zinc on the manganite, probably thus : 

(KE 3 01) 2 Zn + H 2 4 Mn 2 = 2 NH 4 01 + Zn 4 Mn 2 
These experimental facts lead the author to the following theory of 
the action of the cell : 

Primary action: — Formation of hydrogen manganite and zinco- 
diammonium-chloride. 

+ 

Mn 2 4 -f 2 HNH 3 01 + Zn 

become Mn 2 4 H 2 + (NH 3 01) 2 Zn. 

Secondary actions, causing polarization. — The hydrogen manganite acts 
locally upon the zinco-diammonium- chloride solution, and forms zinc 
manganite and ammonium chloride ; this proceeds more rapidly by gal- 
vanic action when the cell is at work, thus : 

— + 

Mn 2 4 + Zn (NH 3 01) 2 + Zn 
become Mn 2 4 Zn (NH 3 01) 2 Zn. 

The zinc manganite and the hydrogen manganite by coating over 
the manganese dioxide, protect it from the primary action of the am- 
monium chloride and zinc, and thus cause polarization of the cell. 

Secondary actions, causing depolarization. — The ammonium chloride 
dissolves manganous and zinc oxides out of the manganite, the manga- 
nous oxide liberating ammonia : 

Mn 2 4 Zn -f 4 01 H 4 N = Mn 2 + 2 0H 2 + 01 2 Mn + (NH 3 01), Zn + 

2NH 3 . 

The manganous chloride dissolves in the presence of the free ammonia 
as a double chloride of manganese and ammonium. By the solution of 
these oxides the manganese dioxide of the manganite becomes active 
again. The depolarizing action proceeds slower than the polarizing, 
and therefore the battery requires to be left uncircuited, in order to 
recover its full power after use. (Chem. News, xlyi, p. 259.) 

Atomic Weights of the Elements. 

Carbon.— Eoscoe has redetermined the atomic weight of carbon by 
the direct combustion of the diamond. If O == 15.96, he obtained as a 



4 SCIENTIFIC RECORD FOR 1882. 

mean of six experiments C — 11.9757. Dumas and Stas in 1840 ob- 
tained 11.9708. (Comptes Rendus, civ, p. 1180.) 

Uranium. — Zimmermann has prepared metallic uranium by Peligot's 
method and studied its properties. Its specific gravity is 18.685, and 
its specific heat between 99° and 0° is .02765 ; the latter number multi- 
plied by 240 gives a product of 6.64, which agrees with the mean atomic 
heat indicated by Dulong and Petit' s law. This settles the controversy 
concerning the correct value in favor of 240 and in accordance with 
Mendelejeff's classification. (Berichte d. chem. Ges., xv, p. 847.) 

Glucinum. — Dr. James Blake thinks that the evidence derived from the 
physiological action of the salts of glucinum may be of use in determin- 
ing its true position among the elements. He finds that the effects pro- 
duced by the introduction into the blood of salts of Be are the same as 
those caused by the salts of alumina and of ferric oxide. He regards 
glucinum as a member of the aluminium group of metals. ( Chem. News, 
xlv, p. 111.) 

Aluminium. — The atomic weight of this element has been subjected 
to a painstaking revision by Prof. J. W. Mallet. The general mean of 
30 experiments gives Al = 27.032, with a probable error of =t 0.0045. 
[Oxygen = 15.961.] (Chem. News, xlv, pp. 256 et seq.) 

Rubidium. — Charles T. Heycock has redetermined the atomic weight 
of rubidium with the view of testing its relation to Prout's hypothesis. 
The figures obtained by titration of the chlorine in pure chloride of 
rubidium are 85.344; and those by titration of the bromide are 85.387, 
results which lead the author to the conclusion that at present rubidium 
cannot be regarded as conforming to Prout's hypothesis. (Report of 
British Assoc., in Nature, xxvi, p. 467.) 

Didymium. — Brauner has determined the atomic weight of didymium 
as 146.18, and that of lanthanum as 138.88. (J. Chem. Soc., xli, p. 68.) 

Yttrium has been prepared by Oleve free from terbium and its atomic 
weight redetermined. He assigns the value 88.9 to Y'" when 0= 15.9633. 
(Comptes Rendus, December 11, 1882.) 

Thorium. — L. F. Mlson has redetermined the atomic weight of tho- 
rium by ignition of the carefully purified sulphate: Th (S0 4 ) 2 .9 H 2 0, 
and obtains as a mean of ten experiments 232.40. (Berichte d. chem. 
Ges., xv, p. 2519.) 

A recalculation of the atomic weights, by Prof. E. W. Clarke. — Brief 
mention must be made in this connection of the systematic recalculation 
of the atomic weights carried out by Professor Clarke and published by 
the Smithsonian Institution as Part Y, of the Constants of Nature. 
Chemists are under great obligations for this invaluable treatise. 

Composition of the Atmosphere. 

Several chemists have carried on independently more or less elaborate 
researches on this subject. Eeiset has made numerous determinations 
of the amount of carbonic anhydride in the atmosphere, and finds the 



CHEMISTRY. 5 

values usually given (4 to 6 volumes in 10,000) much too high. He gives 
2,962 vols, in 10,000 as the mean of 220 experiments made near Dieppe. 
The ratios obtained in Paris are somewhat higher, being 3,168 vols, of 
carbonic anhydride in 10,000 of air. ( Ann. Chim. et Phys. (5) xxvi, pp. 245 
et seq.) 

A. Muntz and E. Aubin have also made determinations of the pro- 
portions of carbonic anhydride in the atmosphere at Paris and near 
Vincennes, and the results (which confirm Beiset's figures) show that 
the variations in the amount of carbonic anhydride are due to local in- 
fluences, and that in general the heavier gas is quite uniformly distrib- 
uted throughout the lower strata of the atmosphere. These chemists 
also examined the air of elevated regions, conducting experiments at 
the altitude of 2,877 meters (9,422 feet) in the Pyrenees. Although the 
direction of the wind and state of the atmosphere varied greatly during 
their experiments, the proportion of carbonic anhydride was found to 
be constant, being about 2.86 vols, in 10,000 of air. For the sake of 
comparison the air was examined, in two valleys at the foot of the 
Pyrenees, one near Pierrefitte (507 meters above the sea-level) and the 
other near Luz (730 meters) ; at the first station the air was found to 
contain 2.79 vols, of carbonic "anhydride in 10,000, and at the second 
2.69 in 10,000, the latter determination being made in the midst of lux- 
urious vegetation. Muntz and Aubin conclude that carbonic anhydride 
is very uniformly distributed throughout the atmosphere, and regard 
their results as confirming Eeiset's statements and Schloesing's theories 
concerning the circulation of carbonic anhydride upon the surface of 
the earth. (Comptes Rendus, xcin, p. 797.) 

Dr. Edward W. Morley has devised a method for accurate and rapid 
analyses of air, and has made a series of daily analyses in duplicate of 
air collected at Hudson, Ohio, for six months, beginning with January 
1, 1880, and one for six months and twenty days, beginning October 1, 
1880. For details of the apparatus and process we refer to the original 
paper. Each pair of analyses occupied about 70 minutes of time, and 
the mean error of a single analysis for half a month was less than the 
thousandth part of one per cent. By comparing the results of this long 
series of daily determinations with the data obtained from the thrice- 
daily maps of the state of the weather furnished by the United States 
Signal Service Bureau, Dr. Morley finds that most of the variations in 
the amount of oxygen are caused by the vertical descent of air from 
high elevations. This descent of cold air seems to be the effect of 
sudden and severe depressions of temperature rather than the cause ; 
the descent follows the cold by a day or two, and the decrease in amount 
of oxygen begins simultaneously with the descent from above. (Proe. 
Am. Assoc. Adv. Sci., 1881 ; abstract in Chem. News, XL, pp. 245, 284 et 
seq.) 



b SCIENTIFIC RECORD FOR 1882. 

List of New Elements announced since 1877. 

The six years ending in 1882 have been unusually prolific in new- 
elements, or at least in announcements of the same, for it must be con- 
ceded that most of them will fail to stand the test of more thorough 
investigation. These alleged discoveries are widely scattered in pe- 
riodical literature, and the following list may prove useful for reference: 

List of elementary substances announced from 1877 to 1882. 



Date. 


Name. 


Source. 


Discoverer. 


1877 
1878 

1879 

1880 

1881 
1882 

i 


Neptunium 

Lavoesium 

Mosandrum 

Davyum 

"New earths " 

"X" 

Philippium 

Decipiuni 


Columbite 


Hermann. 

Prat. 

J. L. Smith. 

Sergius Kern. 

Gerland. 

Soret. 

Delafontaine. 

Delafontaine. 

Marignac. 

Nil son. 

Dahll. 

Guyard. 

Leeoq de Boisbaudran. 

Wagner's Jahresbericht. 

Cleve. 

Cleve. 

J. L. Smith. 

J. L. Smith. 

Scacchi. 

Kaemmerer. 

Marignac. 

Phipson. 

Cleve. 


Pyrite 




Platinum ores. 


Unnamed mineral 

Gadolinite 


Samarskite 


Samarskite 


Ytterbium 

Scandium 




Gadolinite 


Norwegium 

Uralium 

Samarium 

Barcenium 

Thulium 






Samarskite 

(Misapprehension) 

Gadolinite - 

Gadolinite . 


Holmium 




Samarskite 


Samarskite 






Comesium 

YaandYtf 


Gadolinite 


Zinc ores 


Didymium^ 


Gadolinite 





New Elementary Substances. — At the meeting of the Russian Chemical 
Society held October 20, 1881 (and reported in the Bulletin de la Societe 
CMmique de Paris, for August, 1882), Mendelejeff, the distinguished au- 
thor of the periodic law, remarked that only two of the recently an- 
nounced elements — scandium and ytterbium — had been satisfactorily 
confirmed. These have been obtained in a pure state by Nilson, and 
neither of them has absorption spectra. All the other metals seem to 
be mixtures, as was the case with the old erbium of Bunsen and Bahr, 
and which proves to contain Sc, Yb, Er, Tr, and other elements. Scan- 
dium corresponds in its atomic weight and properties to elcabor, a hypo- 
thetical substance, the existence of which had been foreseen by the 
speaker. 

Mendelejeff expressed himself convinced that his periodic law will find 
further confirmation in the results to be yet obtained in studying the 
elements of cerite and of gadolinite. (Bull. Soc. Chim., xxxviii, p. 110.) 

A new element accompanying didymium is announced by the Swedish 
chemist, Prof. P. T. Cleve. He has long studied the rare earths existing 
in cerite, gadolinite, and similar minerals, and the behavior of the oxide 
of didymium obtained from the latter has led him to suspect the presence 
of a new element. In the beginning of the year 1882 he submitted to 
fractional precipitations about 200 grams of didymium oxide, and sepa- 
rated from the yttria earths with potassium sulphate by repeated pre- 
cipitations; the atomic weight of the first fraction was 14G, that of the 



CHEMISTRY. 7 

last 142. The examination of the ignition spectrum of the last frac- 
tion showed, besides strong rays of didymium and lanthanum, new rays, 
among which is a very strong one having the wave-length of 4333.5. This 
ray belongs neither to didymium, lanthanum, yttrium, erbium, terbium, 
nor to Marignac's Ya, and is regarded by Gleve as peculiar to a new 
element which he designates provisionally by Di/3. (Comptes Bendus; 
abstract in Chem. News, xlv, p. 273.) 

Soon after the publication of the above statement by Professor Cleve, 
B. Brauner printed a note in the Chemical News (46, 16),. in which he 
shows that he anticipated the Swedish chemist in discovering a new 
element accompanying didymium in cerite. His experiments were made 
in Professor Eoscoe's laboratory, and some of his results were published 
in the Anzeiger der Tcais. Academie der Wissenschaften (October 6, 1881). 
Brauner thinks that oxide of didymium, as usually known to chemists, 
consists of a mixture of at least three elements, true didymium having 
an atomic weight =145.4, Oleve's element, more basic than didymium, 
and a third with a higher atomic weight is less basic than didymium. 
This last may possibly be samarium. 

Professor Cleve in a still later communication states that continued 
researches by himself and Thalen have convinced him that the ray 
4333.5 belongs to the spectrum of lanthanum, and that the existence of 
a new element is very improbable. (Chem. Neivs, xlvi, p. 43.) 

The earths contained in samarsMte have been studied by Professor 
H. E. Boscoe, with the object of ascertaining the existence or non-ex- 
istence of Delafontaine's philippium. Eoscoe worked up 1,500 grams of 
samarskite and obtained about 60 grams of oxides containing terbium, 
erbium, yttrium, and philippium (?). The oxides were converted into 
formiates, and these salts carefully examined to obtain pure philippiuni 
salt, but the author failed to get an oxide having a constant atomic 
weight equal to 122 (claimed by Delafontaine). The numbers varied 
between the atomic weights of terbia and yttria. Eoscoe then tried the 
following conclusive experiment : 3 grams of terbia, having an atomic 
weight of 147.9, and 3 grains of crude yttria, with an atomic weight of 
101.4, were respectively converted into formiates. Of each of these two 
formiates, two-thirds were brought into solution separately while the 
other third of the terbium formiate was mixed with the remaining third 
of yttrium formiate, and the mixture dissolved. Each of the three so- 
lutions was then mixed with an equal bulk of alcohol and allowed to 
stand for the same length of time. The two solutions, containing re- 
spectively terbia and yttria, gave crystals presenting the ordinary ap- 
pearance of formiates of the metals in question, but the third solution 
containing the mixed formiates deposited rhombic prisms exactly like 
the crystals which Delafontaine claims are peculiar to the formiate of 
philippium. The non-existence of philippium is thus undoubtedly es- 
tablished. (Chem. Neics, xlv, p. 184.) 



8 SCIENTIFIC RECORD FOR 1882. 

Researches on other Elements, etc. 

Thorium. — Two important memoirs have been published by L. F. MI- 
son on thorite and its chief constituent, thorium. He worked upon two 
kilograms of the rare mineral and prepared a very pure thorium sulphate, 
from which he made a determination of the atomic weight of the element. 
(See paragraph on atomic weights.) He determined the specific gravity 
of thoria, finding the figures 10.2199. He also prepared the metal by 
the reduction of potassio-thorium chloride with sodium in the iron appa- 
ratus he had previously used for beryllium. The metal obtained formed 
a gray shining powder showing distinct crystals under the microscope; 
it is unaltered by exposure to air up to 100-120° G. ; when heated higher 
it burns brilliantly, forming a snow-white oxide. The metal burns in 
chlorine, bromine, and iodine gases, yielding sublimates ; it is slowly 
attacked by dilute sulphuric acid, and by dilute nitric ; concentrated 
nitric acid has very little effect. Hydrochloric acid dissolves the metal 
readily. The metal has the specific gravity of about 11, results being 
not perfectly satisfactory. (Berichte d. chem. Ges., XV, pp. 2519-2547.) 

Properties of Pure Metallic Aluminium. — Prof. J. W. Mallet, in the 
course of his researches on the atomic weight of this metal, required a 
quantity in a very pure condition, and this gave an opportunity of study- 
ing its properties. Crude (commercial) aluminium contains: 

Al 96. 89 

Fe. 1.84 

Ou trace. 

Si 1.27 



100. 00 

This was converted into bromide by treatment with liquid bromine* 
and the product purified by fractional distillation. It was then reduced 
by sodium in a crucible lined with a mixture of purified and dried 
alumina, with sodium aluminate. The metallic globules were again 
fused and further purified with hydrochloric acid. The metal thus ob- 
tained was perceptibly whiter than the commercial article, also softer, 
more malleable, and had a fracture with some appearance of fibrous 
silkiness. Its specific gravity at 4° O. is 2.583. Its specific heat is 
0.2253 as a mean for the range of temperature 0°-100° O. Attempts 
were made to roughly estimate the fusibility, and the pure metal seems 
to be a little less fusible than the commercial article. It also presents 
greater resistance to the prolonged action of solvents — acids and alka- 
lies — than the impure metal. (Chem. News, XL VI, p. 178.) 

Iridium, according to Mr. John Holland, can be alloyed with phos- 
phorus at a high heat, and the ulloy fuses at a comparatively low tem- 
perature. The fused metal contains, according to Prof. F. TV. Clarke, 
about 1\ per cent, of phosphorus. The phosphorus is removed by heating 



CHEMISTRY. 9 

in a Hessian crucible with lime. The iridium melted by this process is 
compact and crystalline ; it is harder than the natural metal, being 
nearly as hard as the ruby; it has the color of steel and is not attacked 
by acids. [Che.. . News, xlv, p. 168.) 

Preparation and Properties of Metallic Caesium. — Owing partly to the 
extreme scarcity of material Bunsen's attempts to obtain caesium in me- 
tallic form were unsuccessful, but Carl Setterberg, availing himself of 
the tons of alums obtained in Marquart's establishment as a secondary 
product in the manufacture of lithium compounds from lepidolite, has 
isolated this rare metal and studied its properties. Setterberg prepared 
in 14 days 40 kilograms of rubidium alum and 10 kilograms of caesium. 
He obtained metallic rubidium by decomposing the hydrogen-tartrate 
with calcium carbonate and sugar, in a mercury flask, but attempts to 
prepare caesium by a similar process were futile. By the electrolysis of 
the cyanide of caesium mixed with barium cyanide in the ratio of 4 mole- 
cules to one, Setterberg obtained the metal quite free from impurities. 
Metallic caesium resembles closely the other alkali metals; is silver 
white, malleable, and very soft at ordinary tern peratures. Thrown 
upon water it floats around and decomposes it with evolution of heat and 
light, in the same manner as potassium and rubidium. It inflames easily 
when exposed to the air unless protected by a film of oxide or by a layer 
of petroleum. The metal melts between 26° 0. and 27° C; its specific 
gravity is 1.88 at 15° 0. Examined in the spectroscope it showed only 
traces of sodium as an impurity. 

Setterberg failed to detect new elementary substances in the residues 
from which he extracted the rubidium and caesium salts. (Liebig's An- 
nalen, ccxi, p. 100.) 

Nascent Hydrogen. — D. Tommasi, by numerous experiments on the 
reducing power of nascent hydrogen, has been led to the conclusion 
that its peculiar power varies with the reaction by which it is generated. 
Hence, hydrogen in a nascent state may be regarded as hydrogen -f 
calories ; or H + a, in which a has different values according to the 
source of the hydrogen ; thus : 

S0 4 H 2 + Zn + aq; a = 38 cal. 
S0 4 H 2 + Cd + aq ; a = 23.8 cal. 
S0 4 H 2 + Mg + aq ; a — 112 cal. 

The hydrogen increases in activity with the increase in value of a $ 
for sodium amalgam it is 112 cal. (Bull. Soc. C/mw., xxxvin, p. 150.) 

Preparation of pure Nitrogen. — Attempts to remove the last traces of 
oxygen from atmospheric air by means of phosphorus, potassium pyro- 
gallate, hyposulphites, potassiumsodium alloy, and red-hot copper prov- 
ing unavailing, Dr. Walter Flight found that it can be effected bypass- 
ing the gas over a large surface of freshly precipitated ferrous hydrate^ 
The latter reagent he prepares by adding a strong solution of 80 grams 



10 SCIENTIFIC RECORD FOR 1882. 

of caustic potash to one of 200 grams of ferrous sulphate. The nitrogen 
thus treated failed to develop a brown color with apotssium pyrogallate. 
(Chem. News, xxv, p. 105.) 

Behavior of Nitrogen in the Distillation of Coal. — Text-books usually 
state that coal contains about 2 per cent, of nitrogen, which conies off 
as ammonia when the coal is heated in closed vessels. Prof. W. Foster, 
however, finds that only a small fraction of the total nitrogen comes off 
as ammonia. In an experiment with coal containing 1.73 per cent, of 
nitrogen, only 14.5 per cent, of this amount was evolved as ammonia, 
1.56 per cent, as cyanogen, 35.26 remained unaltered, and 48.68 of the 
whole amount remained in the coke. (Chem. News, xlv, p. 299.) 

Presence of Arsenic in Bismuth Subnitrate. — Of fourteen samples of 
bismuth subnitrate examined by K. H. Chittenden and S. W. Lambert, 
only one was found to be perfectly free from arsenic. The average con- 
tent of poison in the samples was .013 per cent, or 13 mgms. (about two- 
tenths of a grain) of As 2 3 in 100 grams of bismuth. The subnitrate of 
bismuth is extensively used in medicine, and though it may not contain 
arsenic in sufficient quantity to be in itself injurious, the presence of the 
poison is greatly to be deplored. Fortunately, as the further experi- 
ments of the authors show, the arsenic is not readily absorbed into the 
system when combined with the bismuth preparation. (Am. Chem. J., 
in, p. 396.) 

A new Oxicliloride of Sulphur. — J. Ogier, by heating to 250° C. in 
sealed tubes a mixture of equal weights of chloride of sulphur and 
chloride of sulphury le, obtained the body S 2 OCl 2 ; it forms a dark red 
liquid, boiling at 60° and having a specific gravity at 0° of 1.656. Its 
formation is explained by the equation: 

2 S 2 CI + 2 S0 2 CI = 2 S 2 OCl 2 + S0 2 + S 

It is decomposed by water, forming a precipitate of sulphur, sul- 
phurous anhydride, sluphuric acid, hydrochloric acid, and thio-acids. 
(Bull. Soc. Chim., xxxvn, p. 293.) 

An abundant source of selenium, according to P. Kienlen, exists in 
the crude hydrochloric acid condensed in Glover's towers. The selen- 
ium is derived from the pyrites, and being volatile at a red heat is car- 
ried over by the hydrochloric acid gas during the calcination of the 
salt cake, and condenses in the first recipients in the form of a red- 
dish mud ; this mud, when dried, contains in some cases from 41 to 45 
per cent, of selenium. The author extracts the selenium from this 
deposit by acting upon it with chlorine, which converts it into a tetra- 
chloride, and this, in the presence of water and chlorine, is transformed 
into selenic acid. The acid liquid obtained is then precipitated with 
hydrogen sodium sulphite andpurified. (Bull. Soc. Chm., xxxvn, p. 
441. 



CHEMISTRY. 1 1 

Presence of Tellurium in Copper. — Prof. Th. Egleston has detected 
tellurium in commercial copper to the extent of about 0.1 per cent. A 
surprisingly small quantity renders the copper red-short, and conse- 
quently worthless for rolling. (Trans. Am. Inst. Mining Engineers, Har- 
risburg Meeting, Oct., 1882.) 

Complex inorganic Acids. — Dr. Wolcott Gibbs has published a con- 
tinuation of his remarkable researches on the complex inorganic acids. 
He has demonstrated that inorganic compounds possess an unexpected 
degree of complexity, and has entered a very wide field of research, yield- 
ing a rich harvest. After discussing in detail several phospho-molyb- 
dates, he describes the preparation of the arsenio-molybdate having the 
composition : 

16 Mo0 3 . As 2 O s . 5 (NH 4 ) 2 O. H 2 + 8 aq. 

The study of these two series (phospho- and arsenio-molybdates) 
leads to the following general results : 

1. The phospho-molybdates form a series of which the lowest term 
contains five atoms of molybdic to one of phosphoric oxide, aud the 
highest tweDty-four atoms of the former to one of the latter. 

2. As in the case of the phospho-tungstates, the greater number of 
the molybdenum compounds contain an even number of atoms of tung- 
stic acid. The homologiziug term is, therefore, 2 M0O3 for these cases. 

3. By far the greater number of phospho-molybdates contain three 
atoms of fixed base (old style), or, in more modern language, may be 
considered as derived from acids containing six atoms of hydroxyl. 
Anhydrous compounds of this type occur, and are not always simply 
residues obtained by heating salts which may be considered as acid, as 
containing, for example, 3 E 2 0. 3 H 2 0. It seems, therefore, necessary 
to admit the existence of acide of the general type n M0O3. P 2 5 . 3 H 2 0. 

4. On the other hand, while no single phospho -molybdate containing 
more than three atoms of fixed base for one of phosphoric*oxide has 
been obtained in a state of indubitable purity, there is probably at least 
one salt with six or more atoms of fixed base, viz : 

22 M0O3. P 2 O s . 7 Ag 2 + 14 aq. 

5. Negative evidence concerning the probable non-existence of a 
series of phospho- or arsenio-molybdates containing more than three 
atoms of fixed base, must not be too highly regarded. 

6. As in the case of the phospho-tungstates, there exists a class of 
phospho-molybdates in which the ratio of the number of atoms of base 
to that of the number of atoms of phosphoric oxide is as 5 : 2, the num- 
ber of atoms of molybdic oxide being even. 

Dr. Gibbs presents a series of structural formulae which explain all 
degrees of basicity which appear to be possible under the general con- 
ditions of the problem. For these and other details we refer to his origi- 
nal paper. (Am. Chem. J., in, p. 402.) 



12 SCIENTIFIC RECORD FOR 1882. 

Constitution of Bleaching Powder. — Che mists have devoted much labor 
to the determination of the exact constitution of bleaching powder, and 
have arrived at results expressed in a great variety of formulae. 

Thorpe gives: Ca 3 H 6 O 6 01 4 (= CaCl 2 2 + CaCl 2 + CaH 2 2 + 2H 2 0); 
Eose gives : (Ca01 2 ,Ca 2 O 2 ) 0aO 2 Cl 2 + 4 H 2 0; Kolb after a very thorough 
investigation : (2 CaOiO^HzO), 0aH 2 O 2 . Odling proposed the formula 

^ a \ OC1 

and this view has been quite generally adopted. Stahlschmidt regards 
bleaching powder as calcium hydroxychloride, 

r«f OH 
oa \ OC1, 

i. e.j calcium hydroxide, CaH 2 2 in which one atom of hydrogen is 
replaced by chlorine. 

The question has been again investigated by Dr. Karl Kraut, who 
examined the action of chlorine on lithium hydroxide and obtained a 
compound very similar to the calcium analogue. When chlorine gas 
was brought in contact with the melted lithium hydroxide, the latter 
increased only 1 per cent, in weight in 4 J hours, but by the addition of 
crystallized lithia in such quantities that the mixture contained about 
1.4 per cent. H 2 the action of the chlorine was hastened. The reaction 
is as follows : 

4 LiOH + 2 01 = LiCl -f LiOOl + 2 LiOH + H 2 

This equation was confirmed by analysis of the product. The lithium 
bleaching powder reacts with carbonic anhydride exactly like the cal- 
cium compound, i. e., it is decomposed with liberation of chlorine. It 
also behaves with chlorine just like the calcium compound. Since, how- 
ever, lithium is a mono-valent element, one atom of the metal cannot 
simultaneously bind chlorine and the radical of hypochlorous acid, and 
Odling's manner of representing the constitution of bleaching powder 
is inapplicable. Besides, the lithium bleaching powder contains lithium 
chloride ready formed. The author therefore concludes that bleaching- 
powder is a mixture of calcium hypochlorite, calcium chloride, and cal- 
cium hydrate. (Liebig's Annalen, ccxiv, p. 354.) 

Lead peroxide can be advantageously prepared, according to Fehr- 
mann, by decomposing a concentrated solution of chloride of lead at 50° 
or 60° 0. with a solution of bleaching powder. The latter is added un- 
til the filtrate no longer shows a brown color when tested with an ad- 
ditional quantity of the bleaching powder. The lead peroxide is well 
washed and collected on a filter. It is nearly black, and very pure. 
The acetate of lead does not yield such good results as the chloride. 
(Berichte d. chem. Ges n XV, p. 1882.) 



CHEMISTRY. 13 

Determination of Organic Matter in Potable Water. 

Prof. J. W. Mallet, in compliance with the instructions of the National 
Board of Health, has made a thorough investigation of the chemical 
methods in use for the determination of organic matter in the potable 
waters. Assisted by Mr. W. A. Noyes, Dr. Charles Smart, and Dr. J. 
A. Tanner, he examined the merits and demerits of the " combustion 
process," the u albuminoid-ammonia process," and the " permanganate 
process." The special conclusions as to the combustion process may be 
briefly stated : The combustion itself, carried out according to Frank- 
land's directions, is a process of great delicacy and satisfactory in trained 
hands ; it requires constant practice to secure good results ; the defect- 
ive point is the failure of the evaporation to leave a residue represent- 
ing the original organic matter of the water, a loss in carbon and a gain 
in nitrogen being constant errors ; the dissociation of ammonia salts 
during the evaporation occasions a loss of nitrogen; in the presence of 
nitrates the difficulties of combustion are great and as yet insuperable ; 
finally, the combustion process cannot be considered as " determining" 
the carbon and nitrogen of the organic matter in water in a sense to 
justify the claim of " absolute" value for its results which has been de- 
nied to those of all other methods. 

The special conclusions as to the albuminoid-ammonia process are as 
follows : In the determination of both " free " and " albuminoid " ammo- 
nia there is a loss resulting from imperfect condensation of the ammonia 
during distillation ; when urea is present some ammonia is easily formed 
by boiling with sodium carbonate, and this vitiates the determination 
of "free" ammonia; in the distillation with alkaline permanganates 
the nitrogenous matter sometimes fails to be completely acted upon be- 
fore the contents of the retort is nearly reduced to dryness, and great 
uncertainty results ; the value of the results by this process depends 
more upon watching the progress and rate of evolution of the ammonia 
than upon determining its total amount. 

The special conclusions as to the permanganate process are : The re- 
sults obtained by the Tidy method, and by Kubel's modification of the 
same, differ irregularly, the latter usually giving much higher figures; 
the results obtained by the Tidy process are liable to variations with 
the atmospheric temperature prevailing at the time the process is ap- 
plied; the amount of oxygen consumed cannot be taken as a measure 
either of the organic carbon or of the total organic matter, though a 
general resemblance may be traced between strongly marked results, 
high or low, for the consumption of oxygen on the one hand and inor- 
ganic carbon (by the combustion process) on the other ; the process is 
capable of giving more valuable information by watching the rate and 
progress of the oxidation of organic matter present than by any single 
determination of the absolute amount of oxygen consumed in a given 
time. (Am. Chem. J., IV, p. 341.) 



14 SCIENTIFIC RECORD FOR 1882. 

Use of Quicklime in Blasting. 

An interesting application of the force resulting from the expansion 
due to hydration is recorded in Nature. To obviate the danger at- 
tending the use of explosive substances in coal mines, the following 
process has been successfully employed in Derbyshire; A series of 
holes six feet apart and about three feet in depth are drilled into the 
coal at the proper points ; these holes are then filled with cylinders of 
compressed quicklime, each 2J inches in diameter and 4J inches long ; 
each hole receives seven of these blocks. A groove in each cylinder 
admits the insertion of a J-inch pipe which extends a few inches beyond 
the aperture of the drilled hole ; through this pipe water is forced by a 
small hand pump. Each hole is of course firmly tamped with paper 
and rubbish. Soon after the water is introduced a sound as of escap- 
ing steam is heard, here and there the tamping is blown out, and in a 
few minutes the whole mass of coal is thrown out from the face upon 
"sprags," short timber props placed to receive it. The time required 
in the various operations is as follows : drilling 12 minutes, charging 
4 minutes, watering 2 minutes, total 17 minutes for each bore-hole. 
(Nature, xxvi, p. 298.) 

ORGANIC CHEMISTRY. 

Formaldehyde (or oxymethylene) has acquired great importance within 
a short period, the researches of Baeyer, Wurtz, and others having 
shown that it forms an intermediate product between carbonic acid 
and carbo-hydrates in the physiology of plant-life. It may be regarded 
as the first product of the assimilation of carbonic acid by plants, and 
by simple polymerization and elimination of water, is probably capable 
of producing sugar, glucose, starch, and cellulose. 

B. Tollens has described a convenient method for preparing this sub- 
stance, which is based upon the oxidation of methylalcohol by air and 
incandescent platinum. For details we refer to the original paper. 
(Berichte d. cliem. Ges., XV, p. 1629.) 

Cur cumin and other Substances from Turmeric. — C. Loring Jackson 
and A. E. Menke give the following : Bengal turmeric root is ground and 
treated in an extracter with ligroine to remove turmeric oil, and then 
the curcumin, mixed with a large quantity of resin, is extracted with 
ether and finally purified by crystallization from alcohol. The average 
yield of curcumin was 0.3 of one per cent. The mean of five analyses 
indicates the following composition: 

Carbon 08. 30 

Hydrogen 5. G3 

Curcumin crystallizes from alcohol in stout needles often in radiating 
groups. It has an orange to yellow color with a blue reflex; its ether 
solution fluoresces green ; it melts at 178° C. It is nearly insoluble in 
water, slightly in benzol, readily soluble in hot alcohol, and more read- 



CHEMISTEY. 15 

ily soluble in glacial acetic acid ; dissolved in strong sulphuric acid it 
blackens by charring ; it is readily soluble in alkalies and alkaline car- 
bonates. It forms two potassium salts K 2 C 14 H i2 4 and K C 14 H 13 4y 
as well as calcium, zinc and barium salts, the last named being insoluble. 
By a study of the esters of curcumin the authors definitely establish C 14 . 
H ]4 4 as the true formula. The results of incomplete oxidation are 
most interesting ; by treating an aqueous alkaline solution with potas- 
sium permanganate, not in excess, a strong smell of vanilla was observed. 
Further treatment effected the separation of an oil, gradually solidifying 
in circular groups of radiating needles, and having a strong odor of 
. vanilla. By sublimation and purification of this product, white needles 
of vanillin, melting at 78° C, were obtained. The yield was very smalL 
The authors also show that diethylcurcumin yields by oxidation ethyl- 
vanillic acid. (Am. CJiem. Journ., iy, p. 77.) 

Urea, its Synthesis and its Estimation. — Fenton has succeeded in trans- 
forming urea into cyanamide; the dehydration was effected by niean& 
of sodium in accordance with the reaction : 

2 CON 2 H 4 + 2 Na = 2 CN 2 H 2 + 2 Na OH + H 2 

Prof.W. G. Mixter has succeeded in forming urea by the reaction of am- 
monia on carbonic anhydride at a red heat. The urea forms slowly, 2 
to 3 decigrams per hour, and collects in fine crystals in the cooler parts 
of the tube through which the gases are conducted. He regards the 
formation of urea, as preceded by that of cyanic acid, thus : CO/+ NH a 
= HONO + H 2 O. The cyanic acid probably unites with ammonia in 
the cooler part of the tube to form urea. (Am. Ghem. J., iv, p. 35.) 

J. R. Duggan described a modification of Knop's process of estimating 
urea by the amount of nitrogen evolved on the addition of an alkaline 
hypobromite. His method consists in mixing the urea and caustic soda 
solutions first and then adding the bromine. He employs a caustic soda 
solution made by dissolving 20 grms. of sodium hydrate in 100 c. c. of 
* water $ and with each 20 c. c. of this he uses 1 c. c. of bromine. The re- 
sults are satisfactory. The weight of nitrogen multiplied by 2.143 gives- 
the amount of urea. (Am. Ghem. J., iv, p. 47.) 

Dr. Theodore G. Wormly has also investigated the above method of 
determining urea and finds that only under the following conditions is 
the whole of the nitrogen uniformly set free : 1st. The reagent (hypo- 
bromite) should be freshly prepared ; 2d. The urea solution should be 
wholly added to the reagent 5 3d. The amount of urea operated upon 
should not exceed 1 part to about 1,200 parts of the diluted reagent \ 
4th. When comparatively large amounts of urea are present the sur- 
rounding temperature should not be less than about 20° O. (68° Fah.). 
(Ghem. News, xlv, p. 27.1 

Acrolein Urea. — Hugo Schiff has described under the name acryldiu- 
reide, a body resulting from the union of two molecules of urea and one 
of acroleine: Prof. A. R. Leeds has obtained a body having the same 



1G SCIENTIFIC RECORD FOR 188-2. 

constitution, CO (^N"H) 2 C 3 H 4 . It forms a white amorphous substance, 
slightly soluble in alcohol, ether, chloroform, and carbon-disulphide. 
Dr. Leeds points out some irrational conclusions in SchiiFs paper, and 
accounts for them by presuming that Schiff operated upon imperfectly 
purified material. (Berichte d. chem. Ges. y xv, p. 1159.) 

Synthesis of Uric Acid. — This interesting synthesis has been accom- 
plished by Prof. Johann Horbaczewski. Pure, finely powdered gly co- 
coll (made from hippuric acid) is mixed with ten parts of pure urea (made 
from ammonium cyanate) and heated in a flask to 200° to 230° 0., until 
the material becomes brownish-yellow and viscous. After cooling the 
mass is dissolved in diluted potassium hydroxide, saturated with ammo- 
nium chloride, and precipitated witha mixture of ammoniacal silver 
nitrate and magnesia mixture. The precipitate, which contains the uric 
acid, is well washed with ammonia water and treated with potassium sul- 
phide. The filtrate is then over-neutralized with hydrochloric acid and 
boiled down to a small bulk. The raw material thus obtained is purified 
by solution in potassium hydroxide, and after repeating the operation, 
the yellowish crystalline powder is washed with alchohol, dried with 
carbon disulphide (to remove the sulphur), and finally with ether. This 
purified material exhibits all the properties and reactions of uric acid. 
The author is engaged in a further study of this synthetical reaction. 
(Berichte d. chem. Ges. XV, p. 2678.) 

% 
Synthesis of a new Amido-Acid analogous to Hippuric Acid. — By the 

action of silver glycocollate on benzoylchloride, Th.Curtins has obtained 
three acids, ordinary hippuric acid, hippurylglycocoll, and a third of un- 
known constitution having the empirical formula Ci H l2 N 3 4 . The 
hippurylglycocoll or hippurylamidoacetic acid crystallizes from hot 
water in rhombic tables or needles which melt without decomposition 
at 206°.5 G. The new acid crystallizes in microscopic needles which 
become brown when heated to 230°, and are decomposed at 240° C. 
(Journal prah. Chem. N. -F., xxvi, p. 145.) 

Synthesis of Tyrosine. — Tyrosine forms a crystalline nitrogenous body 
existing in the animal organism (spleen, liver, urine, &c), produced by 
the decomposition of albuminoid substances. It has long been studied 
by chemists j Liebig obtained it by acting on decomposing caseine with 
melted potash, Muller found it in putrefying yeast, Hinterberger pre- 
pared it by boiling oxhorn with sulphuric acid, and its constitution has 
been discussed by several authors. In 1869 L. Barth pointed out that 
tyrosine could be regarded as a parahydroxyphenylainidopropionic acid, 
but his attempts to prepare it, as well as the proposed reactions of Beil- 
stein and Kuhlberg, were unsuccessful. 

Erlenmeyer has been engaged for several years in experimenting in 
this direction, and with tbe assistance of Dr. A. Lipp has at length 
accomplished this interesting synthesis. The* process is as follows : 



CHEMISTRY. 17 

Phenylalanin (phenyl-^-amidopropionic acid) is converted into paranitro- 
phenylalanin by the action of sulphuric and nitric acids, and this product 
is transformed into paraainidophenylalanin by means of tin and hydro- 
chloric acid. The chloride of this diamido compound is treated in 
alcoholic solution with nitrous acid and the resulting body heated with 
water. On evaporating and treating the residue with ether a sirupy 
liquid is obtained which is probably parahydroxyphenyllactic acid. 
This product is supersaturated with ammonia and concentrated by 
evaporation, which gives a crystalline mass showing under the micro- 
scope the crystalline characters of tyrosine. By recrystallizing from 
dilute boiling alcohol the material is purified. Analysis shows it to 
have the exact constitution of tyrosine : 

C 9 H n N0 3 or 6 H 4 J OH 2 CH.NH 2 .COOH 

(Berichte d. chem. Ges., xv, pp. 1006 and 1544.) 

Synthesis of Anthracene and Phenanthrene from Orthobrombenzyl- 
bromide. — 0. Loring Jackson and J. Fleming White, with a view to set- 
tling the exact constitution of anthracene, have studied the action of 
sodium on orthobrombenzyl-bromide, and obtained anthracene and phen- 
anthrene. The former was identified by its melting point (212°), by the 
formation of anthraquinone (melting at 273°), and of alizarine ; the latter 
was identified by the melting point of its quinone, 198°, and by Lauben- 
heimer's test. Dibenzyl also forms in this reaction, and an oil of uncer- 
tain composition, possibly benzyltoluol. 

By this synthesis it is proved that the two connecting carbon atoms 
in the benzol rings are attached to each ring in the ortho-position, and 
the last doubt about the constitution of anthracene is removed. ( Chem, 
News, XL VI, p. 44.) 

Synthesis of Organic Bodies by the Electrolysis of Water and Solu- 
tions with Electrodes of Carbon. — A. Bartoli and G. Papasogli, in re- 
searches on galvanic polarities, had observed that coke, charcoal, or 
graphite, under the action of the current, is disaggregated $ the elec- 
trolyte is blackened more or less, according to its nature and that of the 
carbon, and the gas evolved at the positive pole is below the normal 
volume. The authors undertook the present investigation to ascertain 
what becomes of the oxygen. They experimented with graphite, coke, 
and wood charcoal, purified by chlorine at high temperatures. With 
coke or charcoal as positive electrode and distilled water as electrolyte 
and a battery of 1,200 Daniell cells, they remarked after two days a 
brown color in the electrolyte and an acid reaction. The battery was 
then reduced to 100 Bun sen cells, and ten days later to 20 Bunsen cells 5 
these were in operation for 30 days. The water became black; the elec- 
trode, which weighed about 500 grams, was totally disaggregated, and 
a thick muddy deposit was formed. The electrolyte was found to contain 



18 SCIENTIFIC RECORD FOR 1882. 

mellitic acid and some of its derivatives, such as the hydro mellitic, 
pyro-mellitic, and hydro-pyro- mellitic acids. 

The muddy deposit contained a black substance soluble in hot water 
and alkalies, but insoluble in most mineral acids and in the majority of 
organic solvents. The authors named this body mellogen, since, on 
oxidation, it yields acids of the benzo-carbonic series. It has the com- 
position C 14 H 2 04. (Comptes Rendus, May 15, 1882.) 

Acetoxims. — By the action of acetone on hydroxylamin, Alois Janny 
has obtained the first member of a new series of bodies, for which series 
he proposes the name of acetoxims. This name is applied to bodies 
containing the group = ONOH united on two sides to carbon. When 
only one bond of the carbon group is united to carbon and the other 
to hydrogen, derivatives of aldehyde are formed for which the name 
aldoxims is suggested. 

The simplest body of the acetoxims is dinethylacetoxim, having the 
formula OH 3 — C(NHO) — CH 3 . This is obtained by mixing an aqueous 
solution of hydroxy lamine with acetone and extracting ether, which 
leaves, on evaporation, brilliant white, hard, volatile, prismatic crys- 
tals. It is soluble in water, alcohol, ether, &c, and melts at 59° to 60° 
C, distilling without decomposition at 134°.8 0. It is a neutral sub- 
stance, and has a slight odor, resembling chloral. 

The author has also prepared and studied ethyl-methylacetoxim, 
methylpseudobutylacetoxim, and some analogous phenyl derivatives. 
(Berichte d. chem. 6es. y xv, pp. 1324 and 2778.) 

Diphenylaminacroleine has been prepared by Prof. Albert E. Leeds by 
heating an alcoholic solution of diphenylamine with an excess of acro- 
leine. After a few hours' digestion a heavy red precipitate forms, soluble 
in boiling alcohol, together with a sticky insoluble mass. The latter is 
treated with alcohol and water until it becomes pulverulent and capa- 
ble of being powdered in a mortar. This amorphous substance proves 
to be diphenylaminacroleine (Oi 2 H 10 N)2 3 H 4 . It does not fuse nor 
sublime, but is decomposed, on heating, into a carbonaceous mass. It 
is insoluble in ether, slightly soluble in alcohol and acetic acid, and solu- 
ble in chloroform, yielding a dark red liquid. It could not be obtained 
in crystals. Bromiue converts it into a bromo-compound, also amor- 
phous, and not further examined. 

Homoquinine, a new Alkaloid. — Howard and Hodgkin have obtained 
a new alkaloid from cinchona bark, for which they propose the name 
homoquinine. Its properties are similar to those of quinine, having the 
same specific rotary power, and nearly the same composition, but it 
crystallizes from ether more readily, and differs in the solubility of its 
salts. One part of the sulphate of homoquinine requires more than- 100 
of water for solution. Alcohol of 90 per cent, dissolves 7.G1 parts of 
the alkaloid, a 5 per cent, solution of which shows a rotation of — 158°. 
(J. Chem. iSoc.j xli, p. GG.) 



CHEMISTRY. 1 9 

Iodide of Bismuth and Potassium as a Reagent for Allcaloids. — F. Man- 
gini prepares this reagent by mixing 3 parts of iodide of potassium with 
16 of iodide of bismuth (liquid) and 3 parts of hydrochloric acid. Thus 
prepared it is not decomposed by water and gives characteristic phe- 
nomena with many alkaloids. 

Strychnine, a light-yellow precipitate, limpid solution; after stand- 
ing the precipitate turns dark yellow. One part of strychnine in 500,000 
of water can be detected. 

Brucine, a golden-yellow silky precipitate becoming lighter in color. 

Morphine, a reddish-yellow precipitate disappearing after some days, 
when the liquid becomes canary-yellow. 

Codeine, a yellowish-red precipitate turning brick-red on standing. 

Narceine, a light-yellow precipitate remaining a long time suspended 
in the liquid; it turns reddish-yellow on standing. 

Atropine, a silky precipitate, which settles as a reddish-yellow powder ; 
on standing the precipitate turns canary-yellow and slowly dissolves, 
coloring the liquid golden yellow. 

Aconitine, a flaky precipitate, which settles as a chrome-yellow pow- 
der; no change on standing. 

Nicotine, a red pulverulent precipitate, becoming reddish-yellow. 

Conicine, a red pulverulent precipitate of a more intense color than 
the preceding, and becoming dirty white on standing. 

Solanine, a golden -yellow precipitate forming slowly, and turning 
darker. 

Veratrine, a light-yellow precipitate, turning lighter. 

Quinine sulphate, a brick-red precipitate, turning dirty white. 

Oinchonine sulphate, like the preceding, but darker after standing. 
{Gazzetta Chimica Italiana, 1882, p. 155, and abstract in Bull. Soc. Chim., 
xxxviii, p. 670.) 

Application of Electrolysis to Dyeing. — Dr. Frederic Goppelsroeder, of 
Muhlhausen, has extended the application of electrolysis to the form- 
ation of coloring matters and to the art of dyeing. He has employed 
the galvanic current in producing and simultaneously fixing dyes on 
various textile fabrics, in preventing the oxidation of colors during the 
printing, and in preparing solutions of reduced dye-stuffs, the so-called 
blue-vats. To obtain, for example, an aniline black on a fabric or on 
paper, the stuff is soaked in an aqueous solution of a salt of aniline (the 
chloride is preferred), and then placed on an unoxidizable metallic plate 
connected with one pole of a galvanic battery or with a small dynamo 
machine. A second metallic plate, bearing in relief the design and con- 
nected with the other pole, is then placed upon the stuff. By pressing 
gently and passing the current of electricity a black design is formed. 
Medals and coins may be copied in a similar manner. By drawing lines 
on the paper or fabric impregnated with the aniline salt, with a piece of 
carbon forming one of the poles, or with a non-oxidizable metal, black 



20 SCIENTIFIC RECORD FOR 1882. 

lines are obtained whenever the presence of the conducting carbon per- 
mits the passage of electricity. 

Hydrogen generated at the negative pole may be employed instead 
of zinc, ferrous sulphate, glucose, hydrosulphite, and the other common 
agents, to reduce baths of indigo, of aniline black, &c. A feeble contin- 
uous current gives the best results. The two electrodes must be sep- 
arated completely. Dr. Goppelsroeder expresses the hope that his ex- 
periments may eventually become of industrial importance. (Keprinted 
from V Ulectricien, and communicated by the author.) 

Method and Apparatus for Testing Inflammable Oils. — In accordance 
with the instructions of the New York State Board of Health to its san- 
itary committee, and in response to an order of said committee, Arthur 
H. Elliott has made an exhaustive report on the methods and apparatus 
for testing inflammable oils, with special reference to dangerous kero- 
sene. The investigations were made with the ultimate intention of es- 
tablishing a standard for testing petroleum in New York State. Mr. 
Elliott examined thirteen kinds of testers, including three open testers, 
and some electric testers, and experimented with four different samples 
of oil on each apparatus. His tests show that it is very important to 
know which apparatus has been used when an oil is said to have a given 
flashing point. One of the oils showed a range of temperature from 95° 
to 130° F. The general conclusions to which Mr. Elliott comes are briefly 
as follows : Of all the 13 apparatuses not one can be called perfectly 
satisfactory; open testers are entirely untrustworthy for determining 
the safety of kerosene oil ; of the closed testers the Wisconsin State 
tester, with a few alterations suggested by the author, gives the most 
reliable results. The electric testers are troublesome to keep in order. 
(Second Annual Report of the State Board of Health of New York, Albany, 
1882, p. 449.) 

u Benzol" or "Benzene," a Question in Nomenclature. — Attention is 
being directed to the necessity of greater uniformity in nomenclature, 
especially as regards the important hydrocarbons C 6 H 6 and C 10 H 8 . Ger- 
man, French, and most American chemists designate C 6 H 6 by the name 
benzol (sometimes spelled with a superfluous finale), while English chem- 
ists use the term benzene; in like manner continental chemists name 
Oi H 8 naphthalin, and Englishmen call it naphthalene, 

A few years ago the Loudon Chemical Society issued a six-page pam- 
phlet* to its corps of abstractors giving rules of nomenclature and nota- 
tion, and this has materially aided in securing uniformity. In preparing a 
paper for the Berichte der deutschen chemischen Gesellschaft, on the "Laws 
of Substitution in the Naphthalene Series," Prof. Henry B. Armstrong, 
of the Loudon Institution, employed the customary English terms, and 
desired the publication committee to refrain from changing them. This 
led to correspondence which is published in the Berichte (vol. xv, p. 

* Reprinted in Chemical News (1883), vol. xlvii, p. 15. 



CHEMISTRY. 21 

200). Professor Armstrong objects to the termination ol for hydrocar- 
bons not of the paraffin series, and would restrict it to the alcohols — 
carbinol, phenol, &c. He calls attention to the confusion which results 
from the terms "ethylene," u anthracene," " phenanthrene," on the one 
hand, and " benzol," " toluol, " and " naphthalin " on the other 5 and he 
expresses the hope that the German Chemical Society may unite with 
the London organization in attempting a uniform nomenclature. The 
publication committee of the Berichte approved of an exchange of views 
on the question. 

American chemists are vitally interested, for in this country the oc- 
currence of the petroleum product called benzine complicates the mat- 
ter. While the English custom has much in its favor, the similarity in 
pronunication of "benzine" and "benzene" leads many Americans to 
follow the continental terminology. Consistency is eminently desirable. 
It will be interesting to watch the result of the movement. 

The Berichte d. cliem. Ges. for 1882 contains articles on the nomen- 
clature of special groups. We refer to Herrmann on the nomenclature 
of azo-compounds (p. 813), and to Wallach's paper on the same subject. 
Liebig's Annalen also has a paper, by Aug. Bernthsen, on the nomencla- 
ture of derivatives of carbonic acid. (Liebig's Annalen, ccxi, p. 85.) 

NOTES. 

Black phosphorus is formed, according to Maumene, when phosphorus 
is distilled in hydrogen (made from zinc and sulphuric acid), and not 
formed when the distillation is conducted in carbonic anhydride. The 
black color soon disappears. 

Lecture experiment. — H. Schwarz finds that zinc dust and sulphur, 
when intimately mixed, combine with very great energy, and the experi- 
ment is more brilliant and interesting than the usual one with iron fil- 
ings (or copper turnings) and sulphur. The best proportions are two 
parts by weight of zinc and one of sulphur. The mixture inflames also 
when struck heavily by a hammer, and when ignited in a confined space 
(gun-barrel) explodes with about one-fourth the energy of gunpowder. 

The rare metal vanadium occurs in large quantity, according to Witz 
and Osmond, in the residues of the iron furnaces of Creusot, and they 
describe a process for extracting it on a large scale with a view to its 
industrial applications. 

Solid paraffine has been discovered by Silvestri in basalt. It occurs 
in cavities about a centimeter in diameter, and is nearly identical with 
the paraffine occurring in petroleum. 

Bernthsen has discussed the unsatisfactory nomenclature of the iso- 
meric sulpho-derivatives of carbonic acid, and proposes to call the radi- 
cal =C=S thio-carbonyl, and to name the acids thio-carbonyl acids. In 
like manner we may have for =C=NH imido carbonyl and similar de- 
rivatives. 

Phosphate of chromium, prepared by the action of phosphoric acid and 




22 SCIENTIFIC RECORD FOR 1882. 

sodium hyposulphite ou ehromates of the alkalies, forms a fiue green pig- 
ment, which is proposed by Ad. Carnot as a substitute for the injurious 
arsenical and cupriferous colors. 

Paul Sabatier has published a note claiming priority over A. Colson 
in the discovery of the sylphides of silicium, Si S, and Si SO. 

Oonstantine Fahlberg has patented a process for preparing sulphate 
of aluminium free of iron for the mineral bauxite. The essential point 
in the method is the use of lead peroxide for the removal of the iron ; 
the lead compound being afterwards recovered in a very simple manner. 

Hautefeuille and Chappuis have studied the formation of pernitric 
oxide, and assign to it the formula N 2 6 . 

Cailletet has obtained a crystalline hydrate of phosphoretted hydro- 
gen by strongly compressing the gas in the presence of water and then 
suddenly decreasing the pressure. Hydrates of ammonia and of sul- 
phureted hydrogen have also been obtained by this method. 

Wroblewski, by a somewhat similar method, has obtained a solid crys- 
talline hydrate of carbonic anhydride, Co 2 8H 2 0. 

In a letter to Nature, G. F. Iiodwell revives the controversy concern- 
ing the relative claims of Lavoisier and of Priestley to the discovery of 
oxygen. Rodwell endeavors to give the greater honor to Lavoisier. 

Hydroxylamine is found by G. Bertoni and 0. Rainiondi to be an act- 
ive poison when injected into the blood. Less than 0.2 gram killed a 
medium-sized dog. It also exerts a poisonous effect when introduced 
into the stomach or under the skin. The blood assumes a chocolate 
color and yields on dialysis nitrous acid, an oxidation product of hydro- 
xylamine. 

Two new antiseptics, calcium- and sodium -glycero-borates, have been 
announced by G. Le Bon, and experiments prove their utility. They 
re odorless and without injurious action on the most delicate tissues. 

The discovery of hydr0fy, NE 2 , claimed by Maumeue, has been denied 
by several chemists who repeated the process (action of potassium per- 
manganate on ammonium oxalate) and obtained negative results. 

Bromo -sulphide of carbon has been discovered by Carl Hell and Fr. 
Urech. It is obtained by the direct action of bromine on carbon di- 
sulphide, and forms small brilliant prismatic crystals having the com- 
position C 2 S 3 Br 6 . 

Rose's fusible alloy has been prepared by W. Spring by subjecting the 
constituents (lead, bismuth, and tin) in their proper proportion, to enor- 
mous pressure. Wood's alloy, melting at G5° C. can be obtained in a 
similar manner. The pressure employed was 7,500 atmospheres. 

Metallic uranium, according to Zimmermann, forms a silver- white, 
somewhat malleable metal, very hard, but scratched by steel. It has 
a specific gravity of 18.7. It burns with brilliant light and scintil- 
lations, forming a bulky oxide, it is slowly attacked by warm nitric 
acid and by sulphuric acid, and readily dissolves in hydrochloric. 

The Royal Soc'ety awarded the Davy medal (in duplicate) to 1). Men- 



CHEMISTRY. 23 

delejeff arid to Lothar Meyer for their discovery of the periodic relations 
of the atomic weights. This has drawn out a protest from John A. E. 
Newlands, of London, who claims priority in the publication of the peri- 
odic law, and who produces evidences of his assertion. (Chem. News, 
46, 278.) 

The French Academy of Sciences offer the new Yolta prize of 50,000 
francs to the author of the discovery which shall enable electricity to 
be applied economically in one of the following directions : as a source 
of heat, of light, of chemical action, of mechanical power ; as a means 
of the transmission of intelligence, or of the treatment of disease. 
Competition is open until June 30, 1887, to scientific men of all nations, 
and the award will be decided in December, 1887. 

The German Chemical Society is in a very flourishing condition. At 
the close of 1882 it numbered 2,527 members, of whom 16 are honorary 
and 263 associate members. The Berichte, published annually by the 
society, forms one of the most important of chemical journals ; the two 
volumes issued in 1881 comprise over 3,000 pages, and the volumes for 
1882 attain about the same size. The total income of the society for 
1882 amounted to 56,247 marks, and the expenses for the same period 
were 44,697 marks. 

Necrology. — During the year 1882 the deaths of many eminent chem- 
ists were recorded. Among them may be mentioned : Dr. John W. 
Draper, of New York ; Dr. Henry Draper, of New York ; Prof. Will- 
iam B. Eogers, of Boston ; Dr. John Stenhouse, of Manchester ; Prof. 
Eudolph Bottger, of Frankfort ; Dr. Ludwig Feder, of Munich j Prof. 
A. Popoff, of Warsaw j Prof. Friedrich Wohler, of Gottingen. 



ERRORS AND CORRECTIONS. 
Page 1, 13th line from bottom, the heading should read * e physical and 

INORGANIC CHEMISTRY." 

Page 3, lines 8 and 9, "H 2 4 Mn 2 " should be in one line. 

Page 6, line 19 (middle column of table), for " Gersdorffita " read "Gers- 
dorffite." 

Page 10, line 2, for "apotssium" read "potassium." 

Page 10, 13th line from bottom, for "sluphuric" read "sulphuric." 

Page 10, last line, for "CAm." read "Chim." 

Page 12, line 4, for "Ca 3 , &c," read "Ca 3 , &c." 

Page 12, line 6, for "(2Ca0 1 " "(2CaO" [i. e., dele J. 

Page 15, lines 5 and 6, "C u H u 4 " should be in one line. 

Page 16, line 24, for "Curtins" read "Curtius." 

Page 18, line lb, for "dinethyl-" read "dimethyl-." 

Page 22, line 5, for " sylphides" read "sulphides." 

Page 22, line 17, for "Co 2 " read "C0 2 ." 

Page 22, 17th line from bottom, for "hydrogen" read "hydrazin" 



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